AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

........................................................................................32 4.......................2...........................................................19 3.............................................................................21 3.........24 4..........................................................1 Principle of bipotentiometric indication .....3..............................37 4...8 2.............5 Control paramaters in the coulometric KF Analysis ........................................................................................4 Control parameters in the volumetric KF titration ............................2 The minimum and maximum dosing rate ............0 mg/g ...................................................5 The solvent........................................34 4...5 1.............................33 4...............................................7 2....................1 The influence of atmospheric humidity (drift determination) .2.............2...........36 4............22 3....................4......................................4 Cleaning the coulometric KF titration cell.................12 3 Titration control and end point determination......................9 2......................39 1 ....2 Stoichiometry of the coulometric KF rection ..............3 Concentration determination with Water Standard 10.....38 5 Sampling .........................................................................................................................9 2........................................................................8 2....29 4...............................................................2 Concentration determination with di-sodium tartrate dihydrate.......................................16 3............3 Pyridine-containing reagents .....21 3....1............18 3.............4 1.................................................................13 3.26 4.....................................................................................................3 Secure draining and filling of the titration cell: SOLVENT MANAGER...4......26 4............3 Volumetric KF Titration: Titrant concentration..16 3.................2 Two-component KF reagent ........19 3.....4 Polarization current and end point................28 4..................35 4..3....2........................................................3 Iodine generation................................................................................................................................................................2 When do you have to replace the electrolyte? ........1 An historic overview ............................4.....................2 Reaction rate .........2.......3.3........................................4 Generator electrode without diaphragm .........................................................13 3...............2 The drift ...........................10 2...............4................6 Dissolving capacity of the solvent .......................................................1 The Control Band ....................................11 2..................................27 4...................................20 3...............METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration .....1 One-component KF reagent ....................1 How often should the concentration be determined?..........................1 KF coulometry ...........1 Indication ...29 4.....2 Coulometric KF analysis.....................................................................3 Consequences for practical applications............................................................1.......................................................................................19 3...4 Concentration determination with pure water...5 Application tips ......................3..................33 4..............................................13 3.............................3...5 Cleaning the measuring electrode ..................1......6 Termination parameters for both coulometric and volumetric KF titration...........2..........4 Special reagents for aldehydes and ketones....................1.......1 Filling the coulometric cell ...................................................................................................3 The Cautious start .....1..........1 Titration stand ..2 End point and polarization current........9 2.......................11 2...........................................6..........................................28 4.......1...........................8 2..........1............................................................................................................4.............................................2..........2.................................6 General recommendations ..1.................................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration .................2................1 Volumetric KF reagents...........2...7 2............................33 4....................................................................5 Karl Fischer reagents with ethanol .......................................................................................................14 3..........4 1...........................26 4..........................................................................................2 Working with the coulometric KF instruments ...............4................................................2 The Karl Fischer chemical reaction ....................................1.......................................... The Karl Fischer titration...........................18 3..............5 Limitations for the use of the cell without diaphragm..........................................3 Stirring speed and dispersion of the volumetric KF titrant....6 2 Volumetric and Coulometric Karl Fischer Analyses ....................7 2.................

2 Reaction with water..............................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.............3 Amount of sample .......2 Foods and technical products ...................2 Storing the sample ..........................59 7....67 8...........................................................62 8 Measurement results ..........68 9 Interferences .........4..............................................................................3 Repeatability .....................................................................................................................3 Liquids: Characteristics ........................1.......6 Determination using the drying oven .............................................inorganic ..........86 11...........86 11...1 Effects of temperature................88 11.............................1 Reaction with methanol.1......................................................................................................................5 Determination of water in gases ................................................................4 Liquids: Sample input...70 9.......................1 Taking the sample..1 Solids: Characteristics...................................1............................................................................48 7............................................6...........5 Accessories for sample input .......................................6 Food ..........................70 9..................58 7....................................................................................1 Resolution and detection limit .1 Solid samples.....................................................................77 11...................2 Coulometric methods ...73 10..........1 Liquid samples ..67 8..................2 Purge gas......................1 Organic Chemicals.....................................................................2 Inorganic chemicals ......................................................1 Coulometry...........................................................3......................................................................................................................................................1 Organic and inorganic chemicals ......47 7....4 Lyophilized substance in septum bottles................................................................................................................................................................................................................................1....................................................2 Side reactions ...................................2.............................................2 Solids: Sample input ................75 11 Karl Fischer Titration: The Method at a Glance ....5 STROMBOLI automatic oven sample changer .....................73 10.................................................................................6..45 7 Release of water from the sample ................................40 6 Sample addition ............................................86 11...3 Reaction with iodine ............................................................72 10 Troubleshooting ..........................................................4 Manual Karl Fischer drying oven..................67 8.71 9.......83 11............................................3...........................................................55 7............2..................................................58 7..60 7..................................81 11.........................................................87 11........................................4..................................................................................................................2....................................................................................4.....................................39 5.......87 11...............78 11............................................................................................................................................................................1 Volumetric methods .......................................................................................71 9...........6................................................2 Volumetric Karl Fischer Titration .......................................................................................................6..............................................................................2 Liquid samples ..................2 External extraction .........................3 Technical products – organic ................57 7...........................................................4.....1.......................................3 External dissolution ........................4....2............6......................................90 2 ..............79 11...80 11................................................................................................................................................................70 9..........................................................................................................................................79 11..................78 11.......77 11.......................................................................89 12 Appendix ..........................................................58 7......................1 Internal extraction ..........3 Procedure...............................................................................................................85 11..........80 11....................................................4 Technical products .....................................................43 6.........2 Measurement accuracy..71 9........................................................................5 Additional literature .....................4 Sample preparation and input ..................................................................................................2 Solid samples......................................................................39 5........83 11....................................4........................................................................1...........54 7...................................................................................77 11...................................................................................................49 7.............1 Principle ..4 Example: reevaluation of side reactions .....................................................5 Technical natural products ...................................................................................................................................43 6.................................................................................................................................6 References...................................79 11................................................................................3 Titration Methods ........................................87 11.......

......98 13.......................98 13...98 13.....................95 12...............................1 One-component reagent .......................................................................................3 Standards for Karl Fischer coulometry.98 13..................95 12................90 12.............................93 12................................91 12..........................................4.........................98 3 ...........................................................4............92 12...4..............2 Two-component reagent: ................................................92 12........4 Reagents and solvents for coulometric analysis ......................1 For samples that are soluble in methanol or ethanol .....................1 For samples soluble in methanol or ethanol .95 12........................93 12................................................6.........5 For acids and bases (pH value) ...........................................................................96 12.........................................92 12.................2 For samples that are poorely soluble in methanol or ethanol ..........4 For ketones and aldehydes...............2 Formula for the external dissolution ......5 Water Standards for Karl Fischer volumetric titration..........................................................................................95 12...............6....94 12...............................1 Formula for the external extraction .........3 Reagents for coulometry: ..3 For samples that are insoluble in methanol or ethanol .......................................................................................................................96 12......................4 For ketones and aldehydes.....2 For samples poorly soluble in methanol or ethanol.......................6 Titrants and solvents for volumetric analysis .......4 Safety data for the KF-components and auxiliary solvents: ............................97 13 Hazards and waste disposal tips ............................................................4................6.................................................91 12..........6........................................3 For samples insoluble in methanol or ethanol........................................4.......................................................6...5 For acids and bases (pH value) .........METTLER TOLEDO Good Titration PracticeTM in KF Titration 12........

First diaphragm-less cell for coulometric KF titration. promoted by publications by E. April 1956.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. and solvent dispensing and removal. Jungnickel. respectively.5% and 1%. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). D. Enormous spread of the use of KF titration.0.J. Publication: “The Dead-Stop End Point“. Peters and J. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available. titrant specific standard parameters and LEARN titration. Use of Karl Fischer method spreads. M. DL37 KF Coulometer from METTLER TOLEDO. 2000 2001 2002 2008 4 . First coulometric KF titration instruments are commercially available. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. Improved METTLER TOLEDO DO307 KF Manual Drying Oven. by G. Meyer and C.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Publication: Coulometric Karl Fischer Titration by A. 0. Introduction of less poisonous KF reagents based on ethanolic solution. Automatic KF titration instruments with piston motorized burettes. Publication on stabilized single-component Karl Fischer reagent by E. Pyridine-free KF reagents are commercially available.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. Solid KF Oven Standards with water contents of 5. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm).Direct method”). They replaced the DL18/35 KF Volumetric Titrators. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation.1 mg/g) with test certificate according to DIN 50049-2. Wernimont and F.Boyd [4]. 1. S. Water standards (10. L.0. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. Eberius [3]. First German DIN standard for the Karl Fischer titration (DIN 51777. Hopkinson [2].

Methanol proved to be suitable as a solvent. the maximum reaction rate is reached here and cannot increase further. it only acts as a buffering agent and can therefore be replaced by other bases. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4).. but rather the methyl sulfite ion. Smith. described by the rate constant k. methanol not only acts as a solvent but also participates directly in the reaction itself. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. all the sulfur dioxide is present as methyl sulfite. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1.e. and the faster the rate of the Karl Fischer reaction. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. Bryanz and Mitchell [6] formulated a two-step reaction: 1. the more methyl sulfite is formed by the capture of protons. the 5 . In order to achieve an equilibrium shift to the right. In an alcoholic solution. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1]. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. i. Verhoff and E. I2 + SO2 + 3 Py + H2O → 2. In the pH range 5. Karl Fischer used pyridine for this purpose. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. C. I2 + SO2 + 3 Py + H2O → 2.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. The rate of the Karl Fischer reaction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations.5 to 8.5. At pH values above 8. In an alcohol-free solution. W.

This.C. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. E. pH values less than 4 and greater than 8 should be avoided in practice. diethylene glycol monoethylether) [10. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. ethanol. J. If a methanol-free titrant has to be used (e. On the basis of this knowledge.g. you can use other alkohols such as. This improves the titer stability. for instance.g. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. methoxyethanol. in a titration. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. pungent pyridine. is not a serious limitation because the water concentration in the solvent is usually much less. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration.5 to 8. 2-propanol. Studies by E. This reagent not only replaced the toxic. Methanol should therefore always be present in the minimum required amount. for determination in ketones or aldehydes). With acidic or basic samples. methanol) (e. 6 . however. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine.g. ethylene glycol monomethyl ether. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. this results in a more sluggish endpoint and higher iodine consumption. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. A. Verhoff and E. ROH + SO2 + RN 2.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5.g. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. In 1988.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. and references therein]. and for bases: salicylic acid).

The solvent is methanol.1.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%. You can also use a methanolic solvent mixture specially adapted to the sample as the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. is approximately 0.e. i.5 mg/mL per year in a sealed bottle. where a solution containing iodine is added using a motorized piston burette. 1 mg/mL for samples with a water content of less than 200 ppm. 2 mg/mL for samples with a water content of less than 1000 ppm. Coulometric Karl Fischer Analysis. Suitable for samples where water is present as a major component: 100 ppm . The reagent can be stored for approximately two years.5% 2. sulfur dioxide and imidazole.1 Volumetric KF reagents 2. Suitable for samples where water is present in trace amounts: 1 ppm . dissolved in a suitable alcohol.. The drop in titer. the decrease in concentration.1 One-component KF reagent The titrant contains iodine. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration. 7 .

One-component reagent: The titrant contains iodine. reagents containing pyridine are still used because they are cheaper and can be made in-house. This reagent is declared as “rapid”. pyridine. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. provided that the bottle is tightly sealed. The titrant has a stable titer. HYDRANAL® (Composite 5K and Working Medium K. sulfur dioxide and 2-methoxyethanol. methanol. or an alcoholic mixture. – Titer less stable. from VWR/MERCK) are commercially available to prevent this problem. + Simple handling. titration speed slower. favorably priced. and results in higher titration speed. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. whereas the solvent consists of sulfur dioxide and a base. Two-component reagent: The titrant contains iodine dissolved in an alcohol. such as amines. To improve stability. from Sigma-Aldrich) and e.1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2.g. methanol) and B (iodine. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. 2. High titration speed. Reagents One-component Two-component 2. The titration takes slightly longer than with the standard KF reagent. e. methanol). sulfur dioxide and pyridine. imidazole.g. 2 mg/mL for samples with a water content of less than 1000 ppm. Solvent capacity restricted. One-component reagent: The titrant contains iodine. imidazole. e. As a result.g. dissolved in an alcohol (usually methanol).g. A titration speed two or three times as high can be achieved with the two-component reagent. leading to higher water contents and a vanishing end point. additional water is produced and titrated at the same time. whereas the solvent contains 2-chloroethanol and trichloromethane. Special methanol-free KF one-component reagents such as e.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. stable titer. The solvent contains sulfur dioxide. 8 . The solvent is either methanol or consists of methanol mixtures. Note that it may be necessary to adapt the end point value in the titration method to these reagents.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. These solutions are mixed 1:1 just before use to form the one-component titrant. imidazole and methanol.2 Two-component KF reagent The titrant contains iodine and methanol. dissolved in methanol. increases their lifetime.1. which allow for fast and accurate Karl Fischer titrations.1. The separation into titrant and solvent improves stability of the KF reagents. This special reagent is also suitable for substances that react with methanol. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. Both the components are very stable in storage.

the anode compartment and the cathode compartment.1. The titrant contains iodine and ethanol. 2.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. diethanolamine and ethanol. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. or “inner burette”) incorporated into the glass titration cell. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I . however. The classical coulometric cell consists of two parts. a double pin platinum electrode. 9 . Both parts are separated by a diaphragm. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry. imidazole. The generator is close to the measuring electrode*. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol. two-component.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction.2 Coulometric KF analysis 2. ethanol-based reagents were launched in 1998. whereas the solvent contains sulfur dioxide.2.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol.

I2. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. 96485 C of current are needed. Cathode reaction At the cathode. is the quantity of charge that is transported by a current of 1 ampere in one second. The negative iodide ions release electrons at the anode and form iodine. This is the main product formed.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine.2. I-. it is known that to produce one mole of a chemical substance that requires one electron. as chloroform. i. other solvents such e. 2. To avoid this. C.→ I2 → H2O 10 . the catholyte should be replaced once in two weeks. the positive hydrogen ions are reduced to hydrogen. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. An ammonium salt is added to the catholyte in order to promote hydrogen production. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). hexanol or ethylene glycol may be added. C. The cathode compartment contains the catholyte. releasing two electrons at the anode. In Karl Fischer reaction two iodide ions. imidazole and iodide salts. This can cause the cathode to become black. iodine is generated from iodide by electrochemical oxidation. i. 2 [RN]H+ + 2e. To calculate it. The catholyte is either a manufacturer-specific special reagent. or the same reagent as used in the anode compartment.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. Note that methyl sulfonic acid. used to generate iodine. The value 96845 C/mol is known as the Faraday constant. 1C=1A·1s On the other hand.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte.g. iodine reacts with water. Anode reaction At the anode. present in the anolyte compartment. Subsequently. are oxidized to one molecule of iodine. CH3SO3H. octanol. 2 I. Methanol or ethanol is used as solvent. which subsequently reacts with water. it is necessary to first recall the definition of 1 Coulomb: one coulomb. This consists of sulfur dioxide. Depending on the application.e.e.

this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10. 2.3 Iodine generation Iodine is generated by means of current pulses of 400. etc. the coulometer operates with current pulses of 400 mA. coulometry is designated as absolute method.). Since the molar mass of water is 18. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. no standardization of the coulometric KF reagents is necessary. In addition. Since current and time can be accurately measured.712 C electrical current. the maximum possible current applied by the instrument is 100 mA.015 g/mol. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. For this reason. 300. less than 3–4 μS/cm).2. the current conversion efficiency for iodine production is assumed to be 100%. As a consequence. Nevertheless. 2.2. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). 200 and 100 mA. For an electrochemically optimized Karl Fischer cell.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. hexanol.e. At very low conductivities (i. it is used as a reference method for the determination of water content. 2 x 96485 C/mol is required for 1 mole of water. With standard conductivity values.

it is still possible for a very small amount of iodine to reach the cathode. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. other easily reducible substances such as unsaturated fatty acids.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. This effect is further enhanced by the small dimensions of the cathode.2.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced.. The latter can thus react more efficiently with water. the cathode is a small-size pin). a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i.g. etc. the cell with diaphragm may yield more precise results.acetamides etheric oils and essences . Nevertheless. 2. this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. 12 . for measurement of samples having a very low water content (e.edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface. may also be reduced at the cathode by the formation of water.ethers ketones (with special reagent) . Nascent hydrogen is formed at the cathode. Thus. a different geometry is used for the generating cell without diaphragm. To avoid this concurring reaction. R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. This is a very good reducing agent. and for very accurate determinations. the relative error due to this effect can be minimized by using a larger amount of sample. lower than 50 μg water/sample). However. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment.chlorinated hydrocarbons alcohols . The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . especially when easily reducible.phenols (most) esters .e. In addition. especially for nitro compounds such as nitrobenzene. In practice.

and hence.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled. The resulting titration speed depends on the following factors: . and the addition or production stopped exactly at the end point.1. The control of the titration is only possible if the end point is indicated. there is no free iodine in the titration/anolyte solution. Ideally. iodine should be added or generated as quickly as possible.the viscosity of the solution and its temperature.the termination of the analysis. . • • • As soon as all the water has reacted with iodine. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. A high voltage is necessary to maintain the specified polarization current at the electrode. the water content. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy.1 Indication 3.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry").the stirring speed and mixing of the sample solution.the addition speed or generation rate of iodine . .the reaction rate of the Karl Fischer reaction . constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. A small. there will be free iodine in the titration solution. . 13 .the control algorithm and its parameters. • • As long as the added iodine reacts with the water. When the voltage drops below a defined value. the titration is terminated. 3.

The iodine is present only at low concentration. At the end of the titration: As soon as all the water in the sample has reacted with the iodine. there is no free iodine in the titration/anolyte solution.1. the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. The two negatively charged iodide ions are attracted by the positively charged platinum pin. Above all. where they donate the electrons and form an iodine molecule.e.(to a lesser extent) the type of electrode (i.the solvent or anolyte used in the instrument. Iodide ions. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. i. again. geometry and dimensions of the metal parts) . A voltage of ca. This drop in voltage is used to indicate the end of the titration. free iodine is present in the titration/anolyte solution. • • At the beginning and during the titration: As long as the iodine generated reacts with the water.METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. respectively. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction". which are present in excess in the titration solution. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. It then acquires two electrons and turns into iodide ions (2 I–). 14 . The end point value mainly depends on . . Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. I2. This free iodine gives rise to "ionic conduction". this value depends on the polarization current. no iodine reaches the negatively charged platinum pin.the polarization current. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. Ipol .e. If mixing is poor. 3.

with longer pins.e. In general the larger the platinum surface the smaller the current density. Sensors with short platinum pins (< 3 mm).METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. the polarization current should be set as low as possible.e. The larger the diameter of the pipe. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). This makes it more difficult to stop the titration at the right moment. pin length: 3 . the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. exhibit a larger potential jump and also a higher end point. With use. a double ring or plates instead of rings. Sensors with a large platinum surface. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). e.g. and increases the sensor resistance. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. iodine excess should be as low as possible to get accurate results. The layer is formed during the first ten titrations. With used sensors. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. 15 . and increases the risk of over titration. its surface can easily bond suitable chemical compounds. As a consequence. a layer is formed on the surface of the platinum pin sensor. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. i. and subsequently it remains constant. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. i. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. just after the equivalence point. on the other hand.4 mm. On the other hand. The current density can be compared to a water pipe where a specific water has to flow. However. pin length: 3 to 4 mm. exhibit a smaller potential jump. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor.

Mixing is influenced by the 1. stirring speed. [SO2] .3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations.0 mL 1. point of titrant addition (volumetric KF titration). irregular. [I2] . [H2O] . At the beginning.0 mL In the coulometric KF analysis. Towards the end of the titration. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. the water concentration is lower. and overtitration may occur. 3. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . lower reaction rates are achieved with anolyte solutions that have been used for a long time. the water content is high.the water concentration. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. 2. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent.2 min with a titrant consumption of 2. As a consequence. In the volumetric KF titration.and on the iodine concentration. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition. a large excess of sulfur dioxide is present in the solvent. the titration may also be too slow.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. On the other hand. shape of the vessel (volumetric KF titration). If the speed is too slow. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. Iodine generation or addition is usually the rate determining factor. sulfur dioxide is present in large excess in the anolyte. If 16 . 3. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent.the sulfur dioxide concentration. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant. which gives a high reaction rate. with the twocomponent reagents. It is consumed with each additional measured sample leading to a decreasing dioxide concentration.5 .

17 . the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. If a longer stirring bar is used. Iodine would not be distributed upwards. This is essential for a fast reaction rate and for short titration times. leading to slower addition and longer titration time. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. Furthermore. but rather along the base directly towards the sensor. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. turbulence is not achieved and the mixing effectiveness is lower. the stirring speed is too fast. Bubbles falsify the measured values. Otherwise the sensor may directly detect added iodine.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters.4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal. The dynamic behaviour of the control can be influenced by a variation of the control band.4.1 The Control Band The control band is a modifiable control parameter for both types of KF reagents. The following drawing reveals a schematical illustration of the control band: 18 .

if the polarization current changes. 3. which leads to a stronger reduction of the dosing speed. the end point must be adjusted. Thus. however. The following points represent possible contributing factors: contaminated or old sensors. In particular.g. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up.3 The Cautious start If the water content is very low. In the cautious mode.4. the control reacts more sensitively to potential changes. The maximum dosing rate is dependent on the actual burette size. This is more suited for small water amounts. the titrator automatically issues a warning.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. the titration starts with a slower acceleration (ramp up) than in the normal mode. at higher water contents. 2.e. In this case you can activate the Start: Cautious parameter.4 Polarization current and end point Each end point is valid for a specific polarization current. The closer the potential to the end point. 3. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. the titration starts so quickly that overtitration may occur. i. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. the titration will take too long. if the control band width is decreased.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt. e. Recommendations 1. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. sensors with very short platinum pins (< 3 mm). The end point for a specific polarization current is influenced by the sensor and the solvent. 3.4.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level.. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control. With large amounts of water. 19 .4. Dosing rate (max) = 2 mL/min. the slower is the titrant addition.

5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. • If 1-comp titrants are used. In order to achieve a good repeatability.g. the overall ionic conductivity is decreased. If one-component reagents are used. instead of methanol or ethanol. 20 . If 2-comp ethanolic reagents are used. used as solvent. 2-propanol. This measure allows the system to cope with the reduced conductivity. • • If 1-Comp titrants are used with Ethanol (e. this results in an illdefined titration end point.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. the titration can be accelarated by reduction of the control band to 300 mV. Auxiliary reagents • If formamide is added to the solvent. Therefore it is recommended to decrease the polarization current to about 15 μA. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. setting up of the titrant as 1-comp KF titrant yields shorter titration times. up to 8 mL/min for most 2-Comp 2 titrants. e. 3.4. the system reacts slowly in the case of ethanol based reagents. which will lead to long titration times and to low precision. the sensor current shall be reduced to 15 μA. Composolver E) the standard 1-Comp parameters (cf. • If Chloroform or Xylene is added in order to dissolve oil samples. the titration curve is more or less flat towards the end. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. • If 2-comp titrants are used. the overall ionic conductivity is increased. table) work fine.g. This results in a lower voltage required to maintain the polarization current. Ethanol-based reagents • Compared to the methanol-based reagents.

which is the case in 1-Comp systems. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. 300. the 1-Comp control is suitable for systems that show an oscillating potential behaviour.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. If the titration takes too long. 100 mA) 21 . E E t Oscillating system behaviour. 3. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. an increase of the control band is recommended. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. 200. 3. The minimum dosing rate shall be used to fine tune the final phase of the titration. However the control band shall not exceed the start potential. which is the case in some ethanolic reagents. 2-methoxyethanol. Cautious Generator current: Automatic. 2. where the methanol has been replaced by e. There is no need to accurately adjust the control band to the actual start potential. Fix (400.6 General recommendations 1. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. In most cases 300 – 400 mV are well-suited. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3.4. In general.g.

In addition. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. i. 3.25 µL for a 5 mL burette).e. the slower is the generation of iodine.Fix). the slope of the iodine generation rate is flat at the beginning of the titration. less than 50-100 μg water per sample). pyridine-free reagents with a faster reaction rate. or it can be set to a specific value (“Generator current” . Initially. More specifically. Five termination parameters can be defined in the titration method: delay time.e.e. The closer the measured potential value from the predefined end point is. maximum titration time. Normal: This iodine generation mode is generally used for all water content determinations. The iodine generation starts slowly. relative drift stop. Since the first developed KF reagents reacted slowly.e. then the titration was stopped. and improved KF titration stands (i. Later on. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. the iodine generation is higher than in the cautious mode. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. 2. Cautious: Suitable for samples of low water content (e. 200 and 100 mA. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. tightly sealed stand). Variation of pulse length (time). In particular. This parameter shortens the titration time and leads to repeatable results.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point..g. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter. a delayed switch-off time of 10 to 20 seconds was set at the end point. i. as soon as the was potential value was lower than the set end point during the defined delay time. minimum titration time 22 . The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. iodine is generated by means of current pulses of 400. absolute drift stop. 300. i. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”. pulse frequency and pulse height (mA) are used as variables by the instruments. high resolution burettes (0.

titrant concentration (volumetric) and side reactions. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. easy to understand (volumetric). Thus.m the drift before titration) and the relative drift. The smallest increment must be sufficiently large to compensate the drift. • Advantage: This parameter ensures a high repeatability of the results. Typical delay time: 5 . especially if working with the KF sample oven.g. Typical value for the relative drift stop = 2-5 μg/min (coulometric). 15 s) following the addition or generation of iodine. otherwise the termination criterion will never be reached. After the defined time has elapsed. the absolute drift stop value must be greater than the initial drift.e. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e. Typical absolute drift stop value: 3 µg/min (coulometric). the titration is terminated and the result is printed.Maximum titration time The titration is terminated after the defined time. Disadvantage: The value optimized to the initial drift. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. 23 . otherwise the termination criterion is never satisfied.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. .

1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. you can ignore these traces. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. A relative drift stop of 20 to 30 µg/min shortens the titration time. If the water content is relatively high. but involves a risk that the titration will be terminated a bit too early.e.. This parameter is independent of the the initial drift (coulometric. i. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. • Advantage: This parameter ensures a high repeatability of the results. This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration . you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min). volumetric). and the titrant concentration (volumetric). It is recommended to be used for substances that release water slowly. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). Thus. possibly resulting in poorer repeatability and lower water contents. Maximum titration time for determinations with the KF drying oven When using the drying oven. The final traces are only extracted very slowly. this is the simplest and most universal parameter to use. 3. A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. The vaporization of water is also irregular in the final stages. so 24 . soluble samples You should normally choose the relative drift stop as a termination parameter.6. the drift at the end is often greater than the initial drift. Use the drift/time curve to determine this value. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular.

A combination of the relative drift stop and the maximum titration time has proved effective for such samples. the titration is terminated at the latest after the defined maximum time. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. If the drift stop value is not reached. you should take measures to reduce the drift. (Set the minimum titration time equal maximum titration time). Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. the maximum titration time has proven to be best termination criterion in practice.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. Therefore. If the drift is greater than 10 µg/min. The higher drift is therefore influenced to a large extent by the sample. 25 . Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. It gives you the best accuracy and repeatability of results.

remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent). since cold air cannot absorb as much moisture. however.e. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . However. The air-conditioning system should therefore be equipped with a moisture condenser. it is titrated to dryness during pretitration.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. whereas molecular sieves require temperatures up to 300 °C. Silica gel can be regenerated over night at 150 °C. until it is absolutely free of water. the relative humidity increases.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. The air within the titration vessel also contains moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. the residual moisture dissolves more rapidly into the anolyte (solvent). the higher the atmospheric humidity in the laboratory. the greater is its influence on the results of the Karl Fischer titration. The following rules should be observed: • • Close all openings in the titration stand. This can take 1 . The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. where the relative humidity can achieve values of more than 80%. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. the titrant and the titration stand. Condition the titration cell before use. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. 26 . The drift. This problem is particularly relevant in tropical climates or in coastal regions. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. Briefly. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results.4 weeks (indicated by a colour change of the indicator of the silica gel). i. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. there will be moisture on the glass surface of the titration cell and the inserts. Moisture can enter the sample. In this way. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. When you assemble the titration stand for the first time.1.3 hours. After the anolyte (coulometer) or the solvent (volumeter) has been added.

the drift indicates the quantity of water that enters the titration stand over a defined period. For accurate results.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. and its value is displayed on the screen.(drift * titration time). the KF titrator continuously titrates the water that diffuses into the cell. This is achieved by titration of the dry solvent for a defined time (drift determination). At the start of a sample titration. On the other hand. traces of water will always find a way into the titration cell. t. this water amount is also titrated during analysis. it is necessary to quantify the amount of water entering the titration cell during titration.1. it is also possible to use the value of a previously performed drift determination (“Determination”). or a fixed value can be defined into the titration method (“Fix value”). In the standby titration. On the other hand.2 The drift No titration stand is completely water tight. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. the last measured drift value is automatically stored. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . Therefore. In this respect. Therefore it must be taken into account when calculating the water content. and is given in μg water/minute.

the level of the anolyte increases. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed.The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. In this case. which leads to a higher drift.2 Working with the coulometric KF instruments 4. 100 mL electrolyte solution (anolyte) into the titration cell.Pour approx. 3 . .When a sample is injected into the anode compartment. . some anolyte solutions contain an excess of iodide and the solution has a brown colour. If the level of the catholyte is the same or higher.First transfer 5 mL catholyte to the cathode compartment.1 Filling the coulometric cell • Cell with generator electrode with diaphragm .The generator electrode should dip approx. This can be avoided as it follows: 1. The catholyte always contains traces of water. By ensuring that the level of the anolyte is higher than the one of the catholyte.5 cm into the electrolyte solution. Note: In production. when the drying oven is used. the anolyte should be topped up from time to time with anhydrous methanol. 28 . • Titration cell with diaphragmless generator electrode . Higher anolyte level → low drift Lower anolyte level → drift is high . However. 100 mL anolyte. As soon as the stirrer is switched off. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant. 2.2. . the moisture enters the diaphragm and is slowly released into the anode compartment. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. .5 mm higher than that of the catholyte. the level of the anolyte drops due to evaporation.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4.Take approx.Make sure that the level of the anolyte is approx. you must add some methanol or sample so that the color changes to yellow. a flow occurs from the cathode compartment to the anode compartment.Then fill the anode compartment with approx. . 2. the levels slowly become the same. If this is not the case.

2. . the drift slowly increases. If an electrolyte is used for a long period without replacement. With poorly soluble samples. when using a generator electrode with diaphragm.2.Anolyte solutions (100 mL): after 1000 mg water. If the drift is too high. The higher the level in the anode compartment.g. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 . below 10 μS. and the risk of over titration increases. If the conductivity of the anolyte drops to a very low value. the level of the solvent or the anolyte exceeds the 150 mL mark. e. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. The capacity is monitored by the coulometers (see operating instructions).METTLER TOLEDO Good Titration PracticeTM in KF Titration 4.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. • • • • • 4. the worse the stirring efficiency will be.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. If an emulsion forms in the anode compartment. This can lead to wrong results. it is common use to replace both the anolyte and catholyte at the same time If after adding samples.Catholyte solutions (5 mL): after 200 mg water. A level sensor in the waste bottle prevents from overflow. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. . In practice. This can happen if large amounts of samples of low conductivity are titrated. Any contact with the reagent is avoided during draining and refilling of the titration cell. In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift. It is fully controlled by the titrator. After being used for two weeks.

Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. Step 2: The Anolyte is drained into the waste bottle by applying vacuum. 30 .

An optional reagent exchange set consisting of tubes. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. drying tube and tube holder enables both draining and refilling. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . In this configuration only draining of the titration cell is possible. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air.

Place the empty generator electrode in anhydrous methanol. If immediate use is required rinsing with anhydrous methanol shall be applied.2. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time.This procedure should be repeated at least once. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. . Drying is not necessary if you use it immediately. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. then with anhydrous methanol and dry it as described above. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. • 32 . Methanol flows through the diaphragm and rinses out moisture and contaminants. which leads to a higher drift. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. especially if dirty samples are analyzed. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration.Fill the generator electrode with anhydrous methanol. Moisture and contaminants are rinsed out of the diaphragm. Method B: . the most effective cleaning agent is chromic acid. since it would cause a higher drift value.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. The C30 provides a reagent monitoring routine which is called Reagent Control.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned.Methanol flows through the diaphragm into the cathode compartment. . . Afterwards thoroughly rinse the generator electrode with water. The procedure is identical to that described above. Simple cleaning and drying of the generator electrode Method A: .

while the two-component titrant is rather stable). it is better to determine the concentration every 2 to 4 hours. • Clean the platinum pin with a paper tissue. This also becomes noticeable through a dark coloration of the anolyte at the end point. the indicating electrode does not need cleaning. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. The layer should therefore not be removed by cleaning. The titrant is not chemically stable.5 mol/L sulfuric acid.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. a layer is formed on the platinum surface after the first few titrations.5 Cleaning the measuring electrode Generally. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. e. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. • With heavily contaminated electrodes. 2) Connect the S7 connection of the generator cell with the indication electrode. In this case. the tightness of the titrant bottle and the desired level of accuracy. However. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. the measuring electrode must be cleaned. .2. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned.g. 4. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. repeatable results. 3.3. 2. The Ohmic resistance of the electrode is increased. place the electrode in 0. so that there is a sharp drop in concentration. Their volume increases considerably with temperature. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days).if the desiccant on the titrant bottle is "used up". 4.01 mg/mL per week. This leads to a higher potential jump.if the titrant bottle is not tightly sealed. We recommend to determine the titrant concentration daily. the one-component titrant.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. This is sufficient in most cases. As already described. This test of the complete system by a titer determination is therefore an essential condition for accurate. samples may be deposited on the surface of the electrode. In the global settings within the setup menu of 33 . which prevents a good indication.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. Based on the chemical stability of the titrant. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) . 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped.

thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. i. Add it into the titration vessel. .using the same titration stand with the same volume of solvent.e. Either the user is simply warned or the usage of the expired titrant is blocked. This sample size yields an optimum titrant consumption of 1.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. which prevents the execution of further titrations.3 to 2. Determine the concentration under the same conditions as for sample analysis.66% of water. Na2C4H4O6•2H2O (M = 230.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded.5 mL with a 5 mL burette. 26-50 % of burette volume.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate.e.08 g/mol). - 34 . Determine the weight by back weighing and enter it as sample size.3. Rinse the burette 2 times into a waste bottle before you determine the concentration.04 and 0.Use the optimized METTLER TOLEDO method M301 Weigh between 0. Note: 1. it contains 15. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic. 4. Under normal conditions. Since it slowly dissolves in methanol. Mix for 3 minutes to achieve complete dissolution before you start the titration.: . i. Make sure that nothing adheres to the beaker wall or to the electrode. The plastic tubing is not absolutely water vapor-tight.and at the same temperature. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . 2.

You must perform the determination in pure methanol! Less soluble. You must either change the solvent after every sample or use pure Solvent* for the determination. They are thus protected against the ingress of moisture and can be stored for up to five years. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. The values obtained are approximately 10% too high.3. You must perform the determination in pure methanol! Highly soluble. The water standards are supplied in glass ampoules. mixing time 1 minute. 35 .e. too high titer). you should weigh in 1.g. mixing time 1 minute. e.05 g di-sodium tartrate).0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water.045 g di-sodium tartrate).METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results. You cannot perform more than three determinations in 40 mL of methanol (with 0. mixing time 5 minutes. "HYDRANAL®-Water Standard 10. A cloudy solution will falsify the results (i.0. Partially soluble. This content is confirmed by the test certificate enclosed with every package. Partially soluble. You can only perform one determination in 50 mL of 1:1 mixture (with 0.0 to 1. You can perform six determinations in 30 mL of Solvent* before you need to change it. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. You cannot perform more than one determinations in 40 mL of ethanol (with 0. Highly soluble. 30% too high.05 g di-sodium tartrate dihydrate). mixing time 2 to 3 minutes. The values that are obtained are approx. mixing time 1 minute. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL.3 Concentration determination with Water Standard 10. Less soluble. Thus.5 g of water standard 10. Slightly soluble. mixing time 2 to 3 minutes.0" from Sigma-Aldrich® with 10 mg water in 10 g standard.

Rinse a 10 mL syringe with approximately 1 mL of water standard.01 mg (e. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. 5. 6. You can use a water standard with 1. accurate results. or with a 10.3.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. the whole content of the ampoule is completely drawn into the syringe.01 g as the sample size.0 mg/g water standard. 4. Thus. Use a new ampoule for each new concentration determination. Glass syringes are better. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. Start the titration without any mixing time. 2. with a Hamilton microliter syringe).g. The error is minimized by rinsing and conditioning the syringe beforehand.0 µL deionized water with a 10 µL syringe. 3. To reduce the influence of the atmospheric moisture. The content of an ampoule is sufficient for 3 to 5 determinations.1 mg does not satisfy the requirements for a repeatable titration. In an open ampoule the liquid standard is exposed to air moisture. Start the titration without any mixing time. Determine the weight by back weighing. Inject 1 to 1.4 Concentration determination with pure water General When using pure water to determine the concentration.g. Plastic syringes may introduce a small amount of moisture. The sample should be weighed either using a balance with a resolution of 0.5 mL at a time as an aliquot. Enter 0. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL. A balance with a resolution of 0.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e. a very good deal of practice and precise working is required to obtain repeatable. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. Inject exactly 10. Draw the whole content of the ampoule into the 10 mL syringe. 4. – – – 36 . the water content is increased and thus this will falsify the results.

corn. - 4. fat Oils: edible oil.0 µL. creams. You can use mixture of solvents to achieve complete dissolution. beverages Cosmetics: soaps. Adjust the plunger to exactly 10. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. hydraulic oil. Only freely available water undergoes reaction with the Karl Fischer reagent. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. caramel. Hold the syringe at right angles directly in front of your eyes to read off the value. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. massage oil. ethereal oils Petrochemical products: gasoline. diesel oil. the sample must release water completely. Always use a syringe with a long metal shaft. kerosene Pharmaceutical products: ointments. ester Organic products: urea. However. to avoid touching the glass part. transformer oil. salicylic acid Foods: honey. tar products.5 The solvent To determine the water content in a sample. After setting the volume. jelly bears Starch products: flour. yogurt. fatty creams Waxes. lay it down on the adapter and empty it completely. suppositories Sugar products: jelly. Always add each sample in exactly the same way. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . Solvent Methanol Max. 2. Insert the syringe through the 1 mm hole of the three-hole adapter. Do not warm the syringe. dioxane. it may draw water out of the needle!). You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. emulsions Petrochemical products: crude oil. amount 100% Samples Solvents: toluene.3.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. if it is absorbent. You can get rid of any bubbles in the syringe by expelling the water rapidly. All the screws in the syringe must be tightened securely. noodles. alcohols.

The amount of formamide at 50 °C should not exceed 30%. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: . 4. 2.salicylic or benzoic acid for basic samples. The solvents that are used should contain as few water as possible (< 100 ppm). The solvent for the two-component reagent contains SO2. 38 . 50°C). Once again. This will lead to incorrect results. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. Therefore. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded.e. starch products will not dissolve in it. the titration of subsequent samples will then be very slow. and .imidazole is used for acidic samples. the water will no longer be completely released. you must replace the solvent timely.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. too low water content. formamide effectively extracts water from starch products.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. If acidic or basic samples are titrated. The extraction capacity can be improved by increasing the temperature (e. If exhausted. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life. or by indicating the maximum number of samples to be titrated. i. On the other hand.g. or the titration will take too long and titrant will be wasted. Sugar is the only type of sample that dissolves in formamide. In this case.3. the amount of water in mg which has been titrated. which may be completely expended if you titrate a large number of samples with high water content. it is necessary to replace the solvent timely. 3.

Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. or at least minimize.the most common source of error. 5. 2. i. 5. you should determine its water content as soon as possible. oils. rinse the bottles two or three times with the sample beforehand. In such cases.g. the sample should be larger the more heterogeneous the distribution of the water. the water is not uniformly dispersed. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. With liquid samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. 3. which cannot be mixed as thoroughly as liquids. such as butter. Use sample bottles with small openings to minimize the ingress of moisture. "An analysis cannot be better than the actual sample!" When sampling.e. 4. and thus air moisture can penetrate the plastic and absorbed by the sample. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. the lower the amount of moisture. It floats on the surface or sinks to the bottom. The sample should be taken quickly to exclude. If you have to store the sample. you will no longer be able to determine its true water content. e. you must be extremely careful to exclude atmospheric moisture . Heterogeneous water distribution in samples: In non-polar liquids. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. the absorption or release of moisture. it must contain the same average amount of water as the material as a whole. you should take into account the following points: 1.2 Storing the sample After you have taken the sample.1 Taking the sample When taking samples for water determination. With liquid samples that do not dissolve water such as oils. This can happen when a sample cools and the water solubility is decreased. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol. The sample must be representative. Use bottles with a septum stopper for liquids of very low water content. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. water may be separated from the sample if it is left to stand for a long time. In the case of non-polar solids. 39 .

For coulometric analyses.5 to 2 mg water per sample. because the absorption of air moisture during sampling and sample addition becomes less important.4 500 2 1. Under optimum measurement conditions. This corresponds to 7. and the required accuracy and precision. This corresponds to 0.1 mg water per sample. because the absorption of atmospheric moisture during sampling or sample addition becomes less important. the optimum amount of water is approximately 10 mg per sample.01 10 8 0. If a high level of accuracy is required. sample size Amount of water [ppm] [g] [mg] 1 10 0.0 5000 0. Repeatable results can be obtained even with 0.3 Amount of sample The amount of sample used depends on • • the expected water content.1 to 0. For optimum accuracy with determinations in the range from 1 ppm to 1% water.5 to 17.2 1. A titrant consumption of 0. the accuracy increases with the amount of sample.0 10000 = 1% 0.05 mL is thus still acceptable when using a 5 mL burette.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. and the following minimum sample sizes should be used: Water content Min. 10-50 μg water can be detected if the demand for repeatability is not too high. the accuracy is improved if larger sample amounts are used.1 to 0. In general. it is recommended to use the minimum sample size given in the following table: Water content Min.05 mg water per sample with a titrant concentration of 1 mg/mL.0 For volumetric titrations.1 1.25 100 4 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 . approx. As a rule of thumb.08 50 5 0. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values.0 1000 1 1. the optimum amount of water is in the range from 0. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration.

Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF.METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. Logarithmic scale! 41 . The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. an optimum sample weight range is recommended. 42 . which is accessible in the online titrations screen: Dependent on the expected water content.

creams. toluene. suppositories b c Liquefy the sample in an oven at approx. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. 43 . Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. In the case of a volumetric Karl Fischer titrator. Inject it into the cell using a wide-bore needle. ski wax. honey a Waxy candle wax. This prevents the sample from solidifying in the syringe during the weighing. The syringe is heated together with the wax. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. Low water content Low water content Hygroscopic Viscous Very viscous ointments. Possibly warm the sample slightly to lower the viscosity. edible oils hexane.1 Liquid samples When adding liquid samples. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. In the case of a volumetric Karl Fischer titrator. Fill the 5 or 10 mL syringe with sample after removal of the piston. benzene glycerol. hydraulic oils. 50 °C and fill it into a syringe. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. especially with samples of low water content. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. aqueous emulsions. silicone oil. paraffin.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. yoghurt. you must take suitable precautions to prevent atmospheric moisture from being absorbed. alcoholic beverages methanol.

Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. Replace the syringe with the remaining sample on the balance and back weigh it. you must aerate the bottle with dry air (equalize the pressure). seal it with cotton wool and insert it into the septum bottle using a short needle. use bottles with a septum stopper and pressure equalization. If the sample is hygroscopic or has a low water content (< 1000 ppm). Enter the sample size in the titrator or transfer it automatically. Otherwise when the syringe is removed. the drop will adhere to the septum. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. To avoid this. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. Start the titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Air flows through the molecular sieve into the bottle when you take a sample aliquot. Fill a syringe without a plunger with molecular sieves. Withdraw the plunger and rinse the syringe with the sample by shaking it. Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. Fill the syringe with sample and wipe the needle with a paper tissue. – – – – – – – – – – 44 .

jelly bears. this would lead to an error of 5% to 10%. in a volumetric KF titrator solids can be directly transferred into the titration vessel.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry .when the titration cell is opened to add the sample. e. cellulose powder: – Either weigh the sample in a dry box or extract it externally.g. solid fat: – Grate the product and add the sample with a spatula. The sample should be quickly weighed and added to minimize air exposure. crystalline samples: Weighing boat – Grind hard. 45 . If possible. salicylic acid. e.g. thus. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode.g. For this reason. pulverize less hard samples in a mortar. salts. Hard. chocolate. it should be added under the same conditions as it was transported and stored. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. With an optimum sample size of 1 mg water/sample. about 50-100 μg water enter the anode compartment. fatty e. jellied fruits.g. Sample characteristic Brittle Hard/soft Pourable Procedure e. coarse-grained samples in a closed. depending on the ambient humidity.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. the storage of samples in a refrigerator may cause water to condense. cooled analytical mill. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. For instance. – Add the sample with a weighing boat.

The syringe is heated up together with the wax. Back-weigh the empty weighing boat. Enter the weight in the titrator or transfer it automatically. The water content is often lower atthe surface than inside the sample. Add the sample into the titration vessel. Start the titration. butter.g. suppositories: – Liquefy the samples in a drying oven at approx. Tare the balance to zero. margarine. paraffin. chocolate cream. - 46 . because the water is released if it is pressurized Waxy e. inhomogeneous e. honey. 50 °C and fill them into a syringe. candles. – Add the sample with a spatula. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. Use a weighing boat with attached flexible tubing if necessary. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. ski wax. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e.g. Do not use a syringe. fatty.g. to prevent the sample from adhering to the vessel wall or to the electrode.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft.

coffee beans: Crush in a mixer.g. Fibrous natural products Suspensions 47 .g.g. brittle Viscous Hard. inorganic salts. fatty Mince the product. e. sausage. crystalline products: Pulverize in a mortar.g. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples.g. brittle Moderately hard. meat. then reduce it further with a homogenizer in an external solvent. noodles. The following methods are available: Sample characteristic Very hard Procedure e. fruit juice extracts. This is not the case with solids if the water is bound as.g. hard salts: Grind in a closed. cooled analytical mill. Sample preparation Water: Example: Biological samples First of all.g. e. minerals. dried fruit and vegetables. e. e.g. chocolate. berries: Reduce with a homogenizer in an external solvent. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. solid fat: Grate the product. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. organic salts. e. water adsorbed on surface capillary bounded water (e. jellied fruits.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. e. in plants) Water Example: Sugar. e. grain. it is necessary to crush insoluble solids in order to gain access to the trapped water.: • • • • entrapped water water of crystallization (salts). fatty Soft. e. cheese: Hard. vegetable juices: Reduce with a homogenizer.g.g.

hazelnuts. grinding the sample additionally with a built-in homogenizer (see photos below).9 srel / % 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.8 1.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. You can speed up the extraction of water from the sample by • • In many cases. etc.4 0.4 1. potato chips.0 1.2 1. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.8 4.8 1.5 8.9 0.1 4.1 1.3 1.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 . the homogenizer eliminates the need to use auxiliary reagents such as formamide with. using either methanol or a mixture of it as the solvent.g. sugar.5 1.3 2.4 1.0 7.9 0. heating the solution with a thermostating titration beaker. Water is then extracted providing the mixing time defined in the titration method is sufficiently long. e.1 mg/pc 3.

water is extracted from the sample by means of a defined quantity of solvent of known water content. pepper. 600 ppm). Briefly. butter milk. Pay attention to the water capacity of chloroform (max. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. The extraction of water can be improved • • • by shaking the solution (mechanical shaker. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. curry) for dehydrated products for sugar (total water). edible fat) for natural substances (almonds. 49 . In particular. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. 350 ppm) and toluene (max.

A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight).20 is normally used. For the extraction of tablets. The larger the sample. Add a sufficient amount of sample. or use an ultrasonic bath with heating. A dilution factor of 10 . Shaking is the method generally used for extraction. or use a homogenizer. the smaller the relative error because the total error is calculated with respect to the sample size.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. Step 3: Extraction - Shake. - 50 . the addition of dry quartz sand has proven useful for improving and speeding up the extraction.

51 .1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix. take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm). R: C: B: msol: mext: m: Note: Blank value (water content of the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling. % or ppm). Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.5 0.5 9.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.4 0.3 0.8 54.6 61.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.9 11. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .6 0.6 72. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.3 0. The weight of the solvent (msol).4 4.4 0.4 0.

The amount of sample should also take account of the absorption capacity of the solvent. The water content of the solvent should be as low as possible. 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. by selecting the appropriate calculation (i. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction.e. “External extraction”) in the method function “Calculation”. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. the formula is automatically given. for instance. 2. Chloroform. reaches the saturation limit for water already at 350 ppm! 53 . Note: 1. In particular.

3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content.2 10. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 . in % or ppm. the addition of methanol is not necessary. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. or with a very low water content.8 2. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent).METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.9 5. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results. or with a high water content Pure solvents can be used to dissolve the samples.2 1.

Since you are able to work with larger amounts of sample when working with this technique. Direct titration is not suitable. the error obtained by direct titration if the titration stand is opened to add the sample is too large. 6.g. 55 . 4. Rinse the syringe two or three times in this way. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. Draw 10 . If the solid has a low water content (<200 ppm). Draw an aliquot into the same syringe again.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. On the other hand. the error as a result of opening the titration stand will be between 10 and 30 µg. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. 5. 2. 7.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. the blank value correction is too large compared to the amount of water in the sample. Thus. Determine the weight by back weighing. 7. weigh it and inject it into the septum bottle. biological tissue. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. and too much titrant is consumed. 3. serum.20 mL of anolyte titrated to dryness into the syringe. Determine the weight of anolyte injected by back weighing. In fact. Remove approx. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. because a large sample amount leads to a too long titration time. weigh it and inject it into the titration cell. this error is reduced. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance.

3. Alternative procedure: 1. the final result must be multiplied by 4 (factor f = 4). the water amount in the septum bottle is 4 times larger. 56 . Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. In this way. The water amount in µg is determined. If you know the lyophilized sample amount in the septum bottle. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. The accuracy of a plastic syringe is enough. zero must be entered for the blank value (B). 7. 5. 2. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. 8. 6. then you can additionally calculate the result can be given in ppm. Remove approx. With a standard method calculation and calculate the water amount in µg. Thus. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Since ¼ of the total amount was injected. 4. Rinse the syringe two or three times in this way.METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. because the anolyte titrated to dryness has a blank value of "0".

you should titrate the gas sample directly from the source. .5 Determination of water in gases To determine the water content of gases. If not.As soon as the drift is stable again. The water content in ppm is calculated by entering the volume and the density.CO2 gas can not be titrated directly since iodine reacts with CO2.Turn the three-way valve. . to ensure that the titration is terminated after the maximum time. . you must fill the gas either into special gas sample tubes or into small steel cylinders. Notes . 600 s as termination parameters.g. . Sampling/sample addition . depending on the water content of the gas. . hydrochloric acid. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time. The gas must be directed through a water-dissolving. 57 .Select "Max.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. .Calculate the volume from the time and the gas flow rate. . . .Stop the gas flow after 1 to 2 mL titrant has been consumed.When titrating large quantities of gas in the same solvent.g.Purge the sample vessel and the tubings thoroughly beforehand with the gas.Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e. start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel. Determination . the gas must be directed through the titration vessel for a defined period of time. time" and a "Delay time" of e.Purge the system with the gas before you start the determination. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction.If possible. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations.Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. to prevent the gas from flowing into the titration vessel. water-free absorption liquid in which CO2 itself does not dissolve.With sample vessels the gas amount gas can be determined by differential weighing. .

g. 11 mg/L nitrogen gas from a cylinder: 1. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results. cause side reactions with the Karl Fischer reagent.4 – 8. The water is transferred to the titration cell in a current of dry inert gas (purge gas). Thus.9 166 99.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.5).1 bar (cf. inorganic samples. the oven temperature should not exceed 160 °C. 7. cf.4) A gas stream of approx. e. chapter 7.2 Purge gas Air contains oxygen. 7.0 mg/L Therefore. that release water very slowly.6. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven.1 - The recovery rate is clearly decreasing with increasing gas flow rate.6. For Karl Fischer titration.6. If you use air for organic samples. you should use a two-stage pressure regulator so that the final pressure is in the range 0.1 Principle The sample is heated in an oven. or 2.7 500 97. If you use nitrogen from a gas cylinder. chapter 7. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99.6 Determination using the drying oven This method is suitable for solids and liquids that 1.6. and the amount of water is determined.5 .: o o air with 50% humidity: approx. the purge gases must be first dried before entering the KF oven. for accurate results do not select a too high gas flow rate. which could react with the sample at higher temperatures. causing the water in the sample to vaporize. The purge gases commonly used contain moisture. 58 . Air should therefore only be used for non-oxidizable.

7. deactivate the drift stop).3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. Method 1: The water evolved is continuously titrated After a short mix time (20 . there are two types of anolyte solutions: 59 . i. all the water is vaporized and transferred to the titration cell. deactivate the drift stop). The KF titration is then started. in contrast to other desiccants. Silica gel and molecular sieves have the advantage that they can be regenerated.60 s). In order to avoid the latter you may also use the minimum time as termination parameter. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . Silica gel can be regenerated over night at 150 °C. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. At the end of the titration. 100% Phosphorous pentoxide. whereas molecular sieves requires temperatures up to 300 °C. the vaporization is often very irregular. especially methanol. It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. To ensure that the determination is repeatable.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. In such cases you should use the maximum titration time as termination parameter (i.e. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum.6. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell.80 µg H2O/L 40 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. Silica gel is appreciably better in this respect. In the case of KF coulometers. With some samples the drift at the end of the titration is significantly higher than the initial drift. they are rapidly exhausted.e. 2.e. you should set the maximum titration time as the termination parameter (i. the titration starts and the released water is continuously titrated. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. but their water absorption capacity is low. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. The relative drift stop or the maximum titration time can be used as the termination criterion.

METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e. oven temperature 200 °C: approx.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. 7. 3.5 .e. time Max.2 1. there is a small loss of water. time Max.g. time Max.2 99. Due to the vaporization of the methanol.200 mL/min.2 4. i. time 60 . fibers) or with samples of low water content. and the better the recovery. The procedure for the determination of water content is described in the operating instructions.200 mL/min. i. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99.95 98. Coulomat AG Oven): Anolyte loss at 150 . the recovery is not 100%. the faster the water is titrated.6.1 Briefly: The less methanol is vaporized.g. dedicated anolyte to be used with a KF Oven (e.e.9 2. It has a large glass sample boat capable of holding up to 10 cm3 of sample. This is particularly important with low-weight samples (e.7 99. time Max. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). as well as a gas flow meter. you should replace the anolyte lost through vaporization with new anhydrous methanol. The recovery therefore depends on the amount of methanol vaporized and the method used. time Max. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0. Examples: Sample Result / ppm No.5 mL/hour Anolyte containing ethylene glycol.8 6.g.4. An air pump is available as an optional accessory. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. oven temperature 200 °C: approx.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C. 1 mL/hour – From time to time.9 9.

55% or VWR/VWR/MERCK water standard KF oven 1%. 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. For the same reason. Some samples have surface water that is lost as soon as the oven is purged with dry gas. the evaporated solvent lost in the gas stream has to be replaced. Then. Close the stop cock and purge the "hot zone". . The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. and/or replace the anolyte of the KF coulometer. This leads to a too low result. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. 3. Set a gas flow rate of 150-200 mL/min. If the drift is higher than 15 μg H2O/min. in volumetric KF titration the methanol loss is approx. 10. Open the stop cock. If the drift is constant. the recovery increases to 99. This can happen when the titration is started only after complete evaporation. 61 9. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. If the water is titrated as soon as it begins to evaporate.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. and does not drop into the cathode compartment/ titration cell. Some samples require some time before water starts evaporating. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. For instance. To check the performance of the titrator/drying oven system. bent drying tube. purge the "cold zone". 2. start the titration so that the drift value is automatically entered. you should proceed as follows: 7. evaporated solvent does not condense in the drying tube. replace the silica gel and molecular sieves of the gas drying unit. A large amount of evaporated water cannot be fully absorbed by the solvent. 5. In such cases.7%. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). 6. do not select the parameter "Auto start". If several determinations are performed in the same solvent. 4.

STROMBOLI is completely controlled by the titrator: all the parameters for the determination. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. The sample vials are moved upward into the oven by a lift.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. including the oven temperature. 2. are included in the titration method. 1 During a sample series: 2 3 1.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. The blue rubber cap seals the sample vial tightly against the oven. Besides 14 places for glass sample vials. 62 . The drying oven can be operated in the temperature range from 50 to 300°C. After the analysis. 3. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value. while a glass tube pierces the aluminum foil cover. The oven heats the sample to the set temperature. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer.6.

Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack. The drift value is defined as the moisture entered into the titration cell by the purge gas. This is particularly important with light samples (e.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). This takes 10-20 minutes as can be seen in the following diagram: 63 . the moisture in the empty sample vial has first to be removed.g. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. To determine the drift value accurately. fibers) or with samples of low water content.

at the end of a series the blank value can be measured again and compared with the value determined at the beginning. for example. At the start of the method. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. By performing a drift determination at the end of the series or between several series. If. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. i. With rapidly changing.e. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. If the maximum titration time is used as termination criterion in the method -which is what we recommend.e. the blank value determination also takes the actual drift into account. and thus the moisture adsorbed on the glass walls is not always the same. In the same way. moisture in the sample vial. If this is the case.e. 64 . In this case. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. The optimum blank value is in the range of 70 .e. Thus. The new blank value is automatically used for the blank correction.the analysis times for the determination of the blank value and for each sample are the same. different plastic samples have to be analyzed. The blank value should be determined before each series because the humidity can change. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. they can be measured at different temperatures using the same method. you can check whether the drift is constant and the new drift value can be used for the next series. it is important to use a new sample vial for each blank value determination (i. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396). It is therefore not necessary to perform a drift determination before each series. suboptimum conditions. etc. the moisture content is somewhat lower. If the temperatures of successive loops are different.g. The first sample of the next loop is then transferred into the oven and the water determination begins. the drift value can change with time. one with the same properties as the sample vials into which the samples have been filled in). For each series. The blank value can also vary as a function of temperature. the moisture in the air present in the vial. a blank determination can be performed between two sample loops. This means that the stored drift value of the previous determination will be used. > 15 μg H2O/min). These method templates are based on a dedicated KF method type called ‘Stromboli’. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. you can enter the number of samples the series includes for each loop. Performing the drift and blank value determination In general. To determine the blank value as accurately as possible. gas flow. as well as the anolyte in a coulometric analysis.) are always slightly different. the vial used no longer has the same properties as the "fresh" sample vials. Nevertheless. drift value x time). the method contains a so-called sample loop. whose optimum bake-out temperatures differ. The loops run through one after the other and the samples are processed sample for sample. Important: After a blank value determination.300 μg water.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. In this case. a blank value determination should be performed before each series of samples since the ambient conditions (humidity.

g. bent drying tube. 3. see also list of results). 4. drying and storage). evaporated solvent is not condensing in the drying tube. A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. you can not only determine solids but also liquid samples. In this way. These are partially vaporized (e. motor oil) or completely vaporized (e. This valve shall be used especially if inert gas sources are used. Use the same vials for a sample series as well as for the blank value determination. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. A sudden shutdown of power immediately switches the valve in that way. This test also serves to check the tightness of the oven and the connection tubing 65 . you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. To check the titrator/drying oven system. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. 2. since it provides a leak free inert gas stream during normal operation.55% or VWR/VWR/MERCK water standard KF oven 1%. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. The delivery tube has a T-piece that causes a small leak flow. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. Set a gas flow of 40–60 mL/min. 7. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. and therefore it does not drop into the cathode compartment. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. 5. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. toluene. This has a large effect on the blank value and thus on the result. 6. With STROMBOLI. 8. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

0 Sample size (g) In both cases.5 1.0 2.25 0. Therefore.0 5. with decreasing sample size the relative standard deviation srel becomes worse.0 3. A good repeatability is achieved the sample size is increased particularly for low water content values. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0. 69 . it is necessary to use the optimum sample size in order to achieve precise results.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

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Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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e.Use higher oven temperature .Replace anolyte Amount of sample too small .Lengthen vaporization time (increase t max) .Replace molecular sieves and silica gel in drying tube . 1 mg water per sample is present.Use a different method Oven: water not completely vaporized . .Use t(max) as termination parameter .Replace anolyte .Clean titration cell and generator electrode and dry at 50 – 80 °C .Higher oven temperature .Grease the tapered joints Moisture from cathode compartment and diaphragm .Check whether titration stand is completely tight. . especially at low water content (< 1000 ppm) 73 .Add a small amount of one-component KF titrant to the catholyte.The repeatability is strongly dependent on suitable sample preparation and sample addition.Check whether titration stand is completely tight.Clean the platinum pins of the measurement electrode with paper tissue . Oven: . drift stop .Homogenize sample.Increase value for rel.Measurement electrode is not plugged in .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte . . titration never ends Very long pretitration Poor repeatability Wet anolyte .Increase end point Oven: water vaporizes very slowly and irregularly .Measurement electrode is faulty Titration stand not protected against moisture .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Level of anolyte should be higher than that of the catholyte .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10. increase t(max) Wrong control parameters . drift stop as termination parameter. if possible increase amount of sample Wrong sample preparation and sample addition . Water distribution in the sample is not homogeneous .Increase amount of sample to ensure that approx.g.Use rel.Increase vaporization time.Use smaller sample Long titration time.

if it is defective.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Replace or change the anolyte .0 or 0.Sample not thermal stable: Use lower oven temperature .use a bigger sample size up to 0.Add sample into KF reagents.Too low value: see above “too low value” if this does not help.Replace or repaire generator electrode.Extend tmin (minimum titration time) Incomplete sample addition .Use higher oven temperature .Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits.Lengthen vaporization time (increase t max) . 10 – 15 minutes .Use smaller sample size Values too high The titration was too fast → overtitration . It has no influence to the result.Reduce the value for rel.Use back weighing.Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: . . at 170 °C.Replace anolyte If this doesn’t help. check generator electrode. For samples with very low water content < 30 ppm . Sample not dissolved (emulsion) . drift stop .Use fix generator current 100 mA . do not splash to the walls of the cell.1 mg/g .0. Anolyte has too low conductifity . bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 .2 .Use start cautious Oven: . If the sample preparation and addition is not done carefully.Check drift and blank value .3 g Generator electrode is contaminated The black cover cannot be removed.Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic. Checking drying oven Out of limits.Too high value: see above “too high value” . bad repeatability With water standard 1. contamination with atmospheric moisture occurs. .Replace anolyte . the Coulometer must be adjusted With water Standard KF Oven 1 %.

see above Oven: . 75 .Clean platinum pins of the electrode with a paper towel. e.g.Increase value for relative drift stop. .Increase vaporization time. if possible increase amount of sample. titration never ends Wrong termination parameters . Titration stand not protected against moisture . external extraction. etc. Wrong control parameters .The repeatability is strongly dependent on suitable sample preparation and sample addition.Use "Rel. Low water content (<1000 ppm)! .2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration . Oven: water is not completely vaporized .g.Use higher oven temperature . increase t(max) Long titration time.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker.Replace molecular sieves and silica gel in drying tube .Use t(max) as termination parameter .Use different method. drying oven.Grease the tapered joints Condition Titration stand .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water .Extend vaporization time (increase t max) . drift stop" as a termination parameter.Extend tmax (maximum titration time) . e.Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture .Check and optimize control parameters.Increase endpoint potential Oven: water vaporizes very slowly and irregularly . .Homogenize sample. Water distribution in the sample not homogeneous .Increase oven temperature .Increase amount of sample to ensure 10 mg water per sample.Reduce sample size Poor repeatability of the results Amount of sample too small . . Side reaction of the sample with the KF reagent .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10.Check whether titration stand is completely tight.

Reduce dVmax and dVmax factor. which dissolves the sample.4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results.Replace solvent .Use titrant with 2 or 1 mg/mL Oven: .Change solvent. 15 – 20 minutes .12 g in 40 mL.Reduce the value for rel.55 % at 220 °C.Change solvent or use fresh solvent after every sample.Use higher oven temperature . . Poor sample preparation and addition . bad repeatability 76 .Extend vaporization time (increase t max) .Increase sample size up to 0. The concentration determination is correct only if the di-sodium tartrate has completely dissolved. For samples with low water content < 400 ppm . If the sample preparation and addition is done carefully. Determination of the concentration using di-sodium tartrate or Water Standard 10. Sample not dissolved .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon . No more sulfur dioxide in the solvent .Check drift and blank value . With water Standard KF Oven 5.Replace the solvent frequently.0 is a simpler and a more dependable method.Add chloroform or other solvent to methanol.Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Sample is not thermally stable: Use lower oven temperature . drift stop . 0.Use back weighing.Samples of low water content (<1000 ppm) are always hygroscopic. Di-sodium tartrate has only limited solubility In methanol max. Oven: .Extend tmin (minimum titration time) Incomplete sample addition . contamination with atmospheric moisture occurs.

C20 V11 C0 V2. V4 C20 V15 C20 V0. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine.V3 C20 di-Nitrobenzene.V7 V2.pyren e. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid.V4. nitrobenzaldehyde > C12 Stearyl alcohol. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. C0 V2. V4 C20 V2.V4. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl.V4.V8 C20 V10.V5 C20.g. anthracene. C24 Hydrocarbons > C12 Biphenyl. C0 Sulfur compounds Phenols V0. bitumen V4. e. V3.C22 V16 C0 V10 C0 Nitrocompounds V3.V3.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. C0 V2 C20 V15 Low pKa value: phenol. nitrotoluene.V3. indole.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. o-cresol Side reaction: naphthol. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0. V3.C22 V2. V4 V2. oxalic acid Oxidizable with iodine: ascorbic acid V2. R-I R-NCO Benzophenone Method V2. C0 Peroxides V2.V5 C20 Ethers Linear and cyclic V2. R-Br.1. V5 C20 V2.V4. V3.V5 C20. V4 C20 Mercaptans V0. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 .V3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11. diphenylmethanol Weakly basic pKa >8: Imidazole.: benzamide. anisidine. cresol. naphthalene > C20 Tar.1 Solid samples 11. salicylic acid High pKa value: 2-chlorophenol. toluidine Oxidizable with iodine: aminophenol Method V2.

V8 Cosmetics Creams. creams Suppositories Tablets Lyophilized preparations V2 V4. NaHCO3 Na2CO3 B2O3 . V32 C20. V5 V5 V2 V20 V2 V5 V30. disinfectants Salves. paraffins: shoepolish. V32 C20. ski wax Tar. multipurpose grease V2 V2. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. indicator dyes. V31 C20. polystyrene. 78 . polypropylene.g. ZnSO4 V2. Phosphate. fungicides. C32 Pharmaceuticals Antibiotics. V32 C21. V32 C21. V31 C31.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. herbicides Soluble: wool dyes. V5 V12 V2 V40. Insoluble: pigments.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. V31 C20. Silicon dioxide Silanols R3Si(OH) Na2SO4.: Na3PO4 Silicon oxide. H3BO3 NaOH.1. Na2HPO4 tert. CaO NaCl. lotion Lipstick Soaps Toothpaste V4. NH4NO3 Nitrites NaNO2 11. poly-amides. C34 V2. V31 C32 V2. HBO3 . NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . KJ.C40 V2 Adhesives All-purpose glue. etc. e. C32 V15. C34 V31 C33 V2. V30 Insecticides.1. bitumen lubricating grease.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. NaAsO2 KHCO3 . C34 V2. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2. CaCl2 . polyurethane. dispersion dyes Waxes. etc. V31 C20. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. PVC. KOH MgO. C34 V10 Na2HAsO3 .

coffee beans.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30. instant coffee. noodles.. (V25) V22. potato chips Potato flakes Dough. V21 Mortar. Zwieback Yogurt. almond paste Instant ice tea. hardened fat V4. silk 11. jam Honey. sea salt Total water: plain salt. mixed spice Mustard Adherent moisture: plain salt. pudding powder. margerine. ice cream Dried albumen Powdered milk V2 V13 V2.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. gummi bears.1. rye. V23 Cacao. V23 V30.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. jelly Sugar: adherent moisture Chocolate Spices Pepper. caramel. wood Cellulose powder Wool. jellied fruits. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. wheat.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.1. broth Biscuits. candy.4 Technical products . corn. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. meat spread. sea salt V23 V24. tobacco. curry. tea. mayonnaise Shortening. (V30) Cheese. V23 Vegetable products V22. Zwieback.almonds instant coffee Fats Butter. noodles. plaster. dried vegetables and fruits Hazelnuts. perborates) without brightener Total water V30 V2 11.1. C30 V2 V20 Paper. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 .

dodecane > C14 heavy oil. crude oil. anisole Methyl benzoate.2. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. isobutane. ethyl acetate Methyl chloride. pentane. ethylal. acetic acid > C2 propionic acid. HNO3. paraffin Aldehyde Acetaldehyde. methylethylketone Ketones V10 C10 80 . hexanol. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. toluidine. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. chlorobenzene. chlorotoluene Acetone. xylene C7 to C14 gasoline. methylal C1 to C7 hexane. nitrotoluene.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.2 Liquid samples 11. acetophenone. t-butyl chloride. hexylamine Reaction with methanol: aniline. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. cyclohexane. chinoline Strongly basic: alihatic amines N-butylamine. dioxane. benzene. toluene. petroleum. HCl Nitrobenzene. diamine Easily oxidized with iodine: hydrazine. C1 Sulfurcompounds V1 C1 V0. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. cyclohexene. disulfides sulfonic acids Mercaptans V1.

tinctures Cosmetics: perfume. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk. transformer oil.3.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer. cream. wine. brake fluid.2. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides. sample input and titration methods. liquor Pharmaceuticals: extrakts. 81 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. sunflower oil Pharmaceuticals and cosmetics: ethereal oils. massage oil Vegetable oils Technical oils Hydraulic oil. refer to chapter 11.

120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 .3 Titration Methods 11. These can be also performed using the one-component reagent.3. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.120 s Delay time: 7 seconds.1 Volumetric methods The methods have been developed using 2-component reagents. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 .120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 . dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .10 minutes Direct titration methanol free Titrant: two comp.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. In this case methanol is used as a solvent. Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .

15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 .150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.20 min With drying oven at 160 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate. Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .

3. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate.

Homogenize sample well.5 mm or without needle. napthalene. silk Cheese.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. yogurt Salts. (Select stir time so that sample dissolves completely. In external extraction solvent (methanol.g. margarine Phenols. shoepolish Creams.g. tobacco. pastes Pulverized soluble Salves. potato flakes Tar. Zwieback Dried vegetables and fruits. chocolate Method S1 S1. gummi bears. tea. After sample removal keep sample sealed. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. coffee. S11 S4. cristalline products Wheat. After sample removal keep sample sealed. shake or sonicate. meat grinder. formamide). jelly.4. Pulverize with mixer. honey. creams gel. formamide). S3 S2. 1-decanol.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 . S11 S6. S3 S10. greasy Soft.4. 60° C. for very thick pastes drill hole in bottom of syringe. broth Hardened fat. No further preparation necessary. meat Jellied fruits.4 Sample preparation and input 11. noodles.8 mm ) Fill in backend of syringe Procedure Grind in sealed. Use grate to reduce size. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. S10 S11 S10. bitumen Method S7.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. almonds. cooled analysis mill.) S8 S9 S10 syringe with needle Ø 0. At room temp. Dissolve sample or extract water. S10 S11 S4.) Homogenize sample well. Use syringe with needle Ø 1. S2 S1.1 Solids: Characteristics Property Very hard Hard. 1-decanol. Melt sample. brittle Soft. (Pre-heat syringe with hair dryer or in drying oven. pepper. active ingredients Na-tartrate S9 S12 11. Let solids settle and remove aliquot of remaining solution with syringe. S8 S10 Property Soft. rocks e. wool. paper. SiO2 Salts. S5 S10 S8 Paraffins. Press through small holes e. ice cream. Cut in small pieces with scissors or knife. almond paste. Pulverize with mortar. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. S10 S2. greasy Examples Minerals. Inject into titration cell. Stir. resinous Waxes Examples Butter. or up to approx.: CaCO3 .

after-shave Beverages. petroleum. Hygroscopic sample or low moisture content (< 1000 ppm) .8 mm) Inhomogeneous emulsions .The pressure loss during sample removal must be compensated with dried air. For each titration use 1 mL syringe (with needle Ø 0.Keep sample in a septum flask. synthetic enamels.Homogenize thoroughly by shaking or stirring prior to sample removal.8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 . L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0.Remove sample immediately.15 °C . crude oil.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. aqueous emulsions Acrylic enamels. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. . acetic acid Silicon oil. H2SO4.8 mm).Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes.Cool sample to approx. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times. 0°C in ice bath. .4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0.4.3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm) Injection with syringe (without or with needle Ø 1. glass Visco-Spoon™ 1 mL ME-71492 1. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 . Boiling point 5 .8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. . . toluene. . gasoline. detergents.15°C Examples Propanol. glycerine Hexane. acetone. milk. 11.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0. glycerine Acetaldehyde Methanol. salad oil Perfume. acetone.4. .4.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.5 mm) Injection with syringe after cooling sample (with needle Ø 0.5 Accessories for sample input Syringe Injection needle Weighing boat.

Chem. Chem. E.. Chem. SEUBERT A.. Electroanal. 460-464 (1982). Anal. 309. Fresenius Z.M.. [8] SCHOLZ.. Chem. Z.. Anal. D. 93. K. VERHOFF. Zweikomponenten Reagentien mit Imidazol“. SCHOLZ. 48. VERHOFF.W. M.. Rotating ring disk electrode meassurement . Anal. Fresenius Z. Part II. Chem. COFINO. „Mechanism and reaction rate of the Karl Fischer titration reaction. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“. Th.. 272 – 274 (1943). 30-32 (1981). J.. E. Electroanal. Both publications from: SEUBERT. 1999 (in German). “Nebenreaktionen in Karl-Fischer-Reagenzien ”. 312. Chem. Anal. [9] WÜNSCH. A.C. Anal.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. 1988 (in German)... J. G. Electroanal.. Chim. Ind. „Wasserbestimmung mit Karl-Fischer-Lösung“. E. W. „Karl-Fischer Reagentien ohne Pyridin. KOK. G. „Karl-Fischer Reagentien ohne Pyridin. BUNSEN.396 (1935). J.. Fresenius J. VERHOFF. Chem. Auflage. HOPFKINSON. BOYD. 123-125 (1981). Chem... „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. “Mechanism and reaction rate of the Karl Fischer titration reaction. Fresenius Z.6 References [1] [2] FISCHER. Soc. R. G. Part I. 139-147 (2000).S. Chem. “Analytical Procedures Employing Karl Fischer Reagent I. M.C. “Untersuchungen zur Karl-Fischer-Reaktion”. WERNIMONT. Verlag Chemie Weinheim (1954) / (in German). Liebigs Ann. J.C. W.. „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. 16-21 (1989) (in German).4.. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”.. Chem. Chem. 203 . J.J. W. Electroanal. P. WÜNSCH. J. Thesis University of Hannover. “Mechanism and reaction rate of the Karl Fischer titration reaction. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. J. 71.. Anal. 15 (4). 86.. 306. 394 . 309. 407-415 (1978). Z. “Mechanism and reaction rate of the Karl Fischer titration reaction. Chem 368. 305-315 (1976). 705-717 (1976). PhD. 334. Amer. Chem. „Karl-Fischer Reagentien ohne Pyridin. First and second order catalytic currents at a rotating disk electrode“. E. „Kinetics and stoichiometry in the Karl Fischer solution“.C. C. G. Rotating ring disk electrode meassurement“. A. Fresenius Z. “Reaktionsmechanismen in der Karl-Fischer-Lösung“. VERHOFF. Part III.. BARENDRECHT. Chem.C. Potentiometric measurements”. Ed. “Mechanism and reaction rate of the Karl Fischer titration reaction.. [10] GRÜNKE.396 (1981). E. J.. SCHOLZ. Part IV. 75-80 (1978). Diploma-Thesis at the University of Hannover / Germany. SMITH. E. Fresenius Z. SEUBERT A. WÜNSCH. MITCHELL jr. J. Fres. E.. 94. E. 215 – 219 (1959).comparison with the aqueous system“. Anal. MEYER. E. Chem. S.207 (1980). GRÜNKE. 265 (1853). Angew. Eng.2412 (1939). Nature of the Reagent”. 395-403 (1977). 61. Fres. Anal. .. BRYANT... BARENDRECHT. Anal. BARENDRECHT. Neue Eichsubstanzen“. Acta. J. 256-260 (1989) (in German). 75. 394 . See literature references in: EBERIUS. Anal. 31 (2). S. “Karl-Fischer Reagentien ohne Pyridin“.. Einkomponenten Reagentien“. 86. J. VERHOFF. Analytical implications”. Anal. F. SCHOLZ. Chem. [3] [4] [5] [6] [7] 87 . Chem. 334. 303. SCHOLZ. Part V. 2407 . 1.

Diploma-Thesis at the University of Hannover / Germany. GIT Verlag GmbH. Food Chemistry 96... DE CARO C. „Untersuchungen einer Karl-Fischer-Reaktion“. M. SCHOLZ. WIELAND. „Wasserbestimmung durch Karl-Fischer-Titration .. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications". Darmstadt / Germany.METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. K. „Karl Fischer Titration“. DE AGOSTINI A. Springer Verlag Berlin. RÜEGG K.. G. Sigma-Aldrich Laborchemikalien GmbH. „Eugen Scholz Reagents for Karl FischerTitration“.Theorie und Praxis“.. SCHÖFFSKI. 1989 (German) 88 .5 Additional literature HYDRANAL®-Manual.A. 431-435 (2006).. E.30918 Seelze / Germany. 1984. D. 2006.. 1985. 11.

89 . For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm). The sample P used for the extraction is not dissolved.1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. % or ppm). WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. WP: This is what we get from the calculation in the KF method.

The sample P used for the external dissolution is completely dissolved into the solvent. Blank value (water content in% or ppm) of the solvent.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample. 90 . Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. Total water content (sample + solvent).3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0. Thus.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial. in % or ppm.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method.01% VWR/VWR/MERCK APURA water standard 0. the total volume is increased.

hydrocarbons (C10 to C20).1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). an emulsion is formed. part of the water content is not measured. ointments. etc. edible oils. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. the water content determined is lower than the actual water content of the sample. This means that if an emulsion is formed in the anolyte. 12. ethers. If the sample does not completely dissolve. the anolyte must be immediately replaced. more solvent can be added to the anolyte. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples.4. acetamide. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. esters. i.4 Reagents and solvents for coulometric analysis To determine its total water content. This is limited to a maximum of 30% to prevent the conductivity from falling too low. nitrocompounds. Alternatively.e. etc.4. the sample must completely dissolve in the anolyte. A number of different anolytes are available to dissolve the various types of samples encountered in practice. In this case.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. alcohols. chlorinated hydrocarbons (up to C10).

This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low. If you measure ketones regularly.4. Chloroform must be added to the anolyte to ensure the solubility of these samples. silicone oils.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences. we recommend the use of a second titration cell. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water. transformer oils.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. hydrocarbons (above C20). For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. etc. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. For cells without diaphragm: - Notes on ketones: - - 92 .4.

etc. e.: - For basic samples. acetic acid.g. The larger the sample. After a longer standby period. the drift is higher because of the very slow side reaction.5 mL.4.5 to 7 (see Section 1. Aromatic aldehydes (e. the substances can. 1 mL). It is important to note that alcohols that react with ketones should not be titrated in this reagent. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. Measure the pH with a glass electrode adjusted with aqueous buffers. Short chain aldehydes (e. the pH value of the anolyte must be adjusted to the range 5. In these cases the pH value of the anolyte should be measured. easily be measured with volumetric KF determination. - For acidic samples. Fill the anode compartment with approx.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. take an aliquot of anolyte from the titration cell.e. i. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. e.g. - - Notes on aldehydes: - - 12. The special reagent for ketones can also be used for other samples. with reactive ketones such as cyclohexanone use only 0. however. Choose relatively small samples (approx. The use of imidazole increases the pH value in the anolyte.g.g.2 mL to 0.2).METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. Use the HYDRANAL® buffer (SIGMA-ALDRICH). It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. 80 mL of anolyte and 20 mL HYDRANAL® buffer. the more important the effect of side reactions becomes. With Karl Fischer titrations of acidic and basic samples. Basic samples must be neutralized with salicylic acid or benzoic acid. benzaldehyde) can also be determined by coulometric KF titration. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). Coulometric KF titration cannot be used to determine these compounds. amines: - 93 . acetaldehyde) are oxidized at the anode with the formation of water. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. To do this. Fill the anode compartment with approx. formic acid. The measurement should not be performed in the titration cell because the electrode introduces too much water.

6.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10). ethers. more solvent can be added to the anolyte 12. This is limited to a maximum of 50%.e. In this case. Alternatively. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. an emulsion is formed. the result determined is lower than the actual water content. The water content is declared on a test certificate supplied with every vial. acetamide.55% (potassium citrate monohydrate).6. the anolyte must be immediately replaced. chlorinated hydrocarbons (to C10). i.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. alcohols. esters. 12. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12. part of the water content is not measured. One-component reagents: 94 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. hydrocarbons (C10 to C20).6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. A number of different anolytes are available to dissolve the various types of samples encountered in practice. edible oils. In this case. etc. etc. ointments.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10.2 For samples poorly soluble in methanol or ethanol These include: etherial oils. If it does not completely dissolve.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. nitrocompounds.

MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. One-component reagents: 95 . silicone oils. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. hydrocarbons (above C20). Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. Chloroform must be added to the anolyte to ensure the solubility of these samples. or an acetal. with the formation of water. etc. transformer oils.6.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12.3 For samples insoluble in methanol or ethanol These include: petroleum oils.6.

g. i.2 mL to 0. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). The special reagent for ketones can also be used for other samples. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference. 80 mL of anolyte and 20 mL HYDRANAL® buffer. however. Coulometric KF titration cannot be used to determine these compounds. The use of imidazole leads to a high pH value in the anolyte. acetaldehyde) are oxidized at the anode with the formation of water. we recommend the use of a second titration cell. 1 mL). Choose relatively small samples (approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. Use the HYDRANAL® buffer (SIGMA-ALDRICH). The larger the sample.g. e. the pH value of the anolyte must be adjusted to the range 5. benzaldehyde) can also be determined by coulometric KF titration. amines: 96 . the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. - For acidic samples.g.e. Fill the anode compartment with approx. With Karl Fischer titrations of acidic and basic samples.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. etc. - Notes on aldehydes: - - 12. It is important to note that alcohols that react with ketones should not be titrated in this reagent.g. In these cases the pH value of the anolyte should be measured. easily be measured with volumetric KF determination. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. If you have titrated a number of ketone samples. e.6. the substances can. Measure the pH with a glass electrode adjusted with aqueous buffers. formic acid. Short chain aldehydes (e. the more important the effect of side reactions becomes.5 mL. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. the drift is higher because of the very slow side reaction. acetic acid. with reactive ketones such as cyclohexanone use only 0. The measurement should not be performed in the titration cell because the electrode introduces too much water. If you measure ketones regularly.2).: - For basic samples.5 to 7 (see Section 1. take an aliquot of anolyte from the titration cell. Aromatic aldehydes (e. To do this.

Irritant when inhaled. Disposal: as an organic solvent. 2methoxyethanol or diethyleneglycolmonomethylether). Fill the anode compartment with approx.3 Reagents for coulometry: Composition: iodine. 13. Health hazard when inhaled. Skin irritant. Health hazard when inhaled. Keep container tightly closed. Do not let reagent contact skin or eyes. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. buffer (imidazole). sulfur dioxide. Keep container tightly closed. Health hazard upon inhalation. The KF solvent contains: sulfur dioxide. tetrachloromethane.2 Two-component reagent: Composition: iodine and solvent (methanol. poisonous when inhaled or swallowed. Keep away from open flames or sparks. swallowed or allowed to contact skin. Poisonous when inhaled or swallowed.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0.: 28 °C MAK value: 100 ppm Flammable. Safety: flammable to extremely flammable. Do not let reagent contact skin or eyes.: 11 °C MAK value: 200 ppm Highly flammable. Ignition temp. 13. iodine. Potential teratogen. swallowed or allowed to contact skin. Disposal: as an organic solvent. Keep away from open flames or sparks.: 87 °C Ignition temp. Ignition temp. Irritant when inhaled.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: .: 46 °C MAK value: 5 ppm Flammable. 2methoxyethanol or diethyleneglycolmonomethylether). 2-methoxyethanol). 2-methoxyethanol. and solvent (methanol. oxidant Ignition temp. xylene or trichloroethaylene). Keep container tightly closed and far removed from open flames or sparks. Do not let reagent contact skin or eyes. 13. Safety: Highly flammable. Ignition temp. Health hazard when inhaled. chloroform. Safety: flammable to extremely flammable. Irritant when inhaled. Disposal: as an organic solvent.1 One-component reagent Composition: sulfur dioxide. swallowed or allowed to contact skin.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. 13 Hazards and waste disposal tips 13. buffer (imidazole) and solvent (methanol. buffer (imidazole) and solvent (methanol.1 ppm.

Ignition temp. Irreversible damage possible. Ignition temp.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled.: inflammable MAK value: 20 ppm Irritant for skin and eyes. Ignition temp. Health hazard upon inhalation 98 .: 6°C MAK value: 20 ppm Extremely flammable. Potential teratogen.: 95 °C Irritant for skin and eyes.

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evaluation. Evaluation of the appropriate titration system (DQ) i. www. Routine operation including PQ.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. specification of the analytical requirements and purchase decision 2. ME-51725145A Markt Support AnaChem . are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. Switzerland Tel.mt.e.com For more information Mettler-Toledo AG. method validation. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. ©09/2009 Mettler-Toledo AG Printed in Switzerland. development of SOPs and maintenance of the validated state of the analytical system. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments.